CN100548470C - The preparation method and the application of the biological sorbing material that seaweed plants and crust amine are formed - Google Patents
The preparation method and the application of the biological sorbing material that seaweed plants and crust amine are formed Download PDFInfo
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- CN100548470C CN100548470C CNB2007101141859A CN200710114185A CN100548470C CN 100548470 C CN100548470 C CN 100548470C CN B2007101141859 A CNB2007101141859 A CN B2007101141859A CN 200710114185 A CN200710114185 A CN 200710114185A CN 100548470 C CN100548470 C CN 100548470C
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Abstract
The invention discloses the preparation method and the application of the biological sorbing material of a kind of seaweed plants and crust amine composition, at first seaweed plants is carried out preliminary treatment with hydrochloric acid solution, lose the swelling behavior in water after making the alginic acid that contains in the seaweed plants protonated, then seaweed plants is pulverized, it can be evenly dispersed in the crust amine aqueous solution.The dispersion of Xing Chenging is after splashing into or clamp-on in the aqueous slkali like this, and crust amine is precipitated, and the seaweed plants that is dispersed in the solution is covered by in the crust amine, and the alginic acid in the seaweed plants is converted into water miscible sodium alginate simultaneously.The present invention is remarkable to the waste water treatment effect that contains heavy metal ion.Crust amine can pass through the chelating Adsorption of Heavy Metal Ions, and the sodium alginate in the seaweed plants can be by forming water-fast salt in conjunction with heavy metal ion, and its adsorbed heavy metal ion can be separated from waste water easily.
Description
Technical field
The present invention relates to a kind of processing technology of biomaterial, be specifically related to a kind of preparation method and application for preparing biological sorbing material by seaweed plants and crust amine.
Background technology
Along with rapid economy development, a large amount of dischargings of waste water, the aggravation of heavy metal accumulation in soil and the water source, the pollution of heavy metal is also serious day by day.Because heavy metal is the biological concentration by food chain easily, constitute serious threat to biological and health.How to administer heavy metal pollution effectively and become the human common problem of paying close attention to.
The governing problem of heavy metal pollution has been done a large amount of research both at home and abroad.The method of wastewater treatment of Application and Development mainly contains chemical method, physical-chemical process and bioanalysis at present, comprises methods such as chemical precipitation, electrolysis, ion-exchange, film separation, activated carbon and silica gel absorption, bioflocculation, biological absorption, plant regulation.Adopt chemical method, physical-chemical process all with the remaining years pollution transportation, easily cause secondary pollution, and be difficult to handle for the harmful heavy metal pollution of large watershed, low concentration.Bioanalysis handles that the heavy metal wastewater thereby cost is low, high efficiency, manageability, non-secondary pollution, help the improvement of ecological environment.In addition, use, can make biology have stronger absorption, flocculation, regulation repair ability, so bioanalysis has vast potential for future development by technology such as genetic engineering, molecular biology.
Summary of the invention
The invention provides the preparation method and the application of the biological sorbing material of a kind of seaweed plants and crust amine composition, the biological sorbing material absorption heavy metal ability of processing by this method strengthens greatly, and stability of material significantly improves.
For solving the problems of the technologies described above, the utility model is achieved by the following technical solutions:
A kind of production technology of seaweed bio sorbing material is characterized in that: comprise the steps:
A, be the hydrochloric acid solution immersion treatment of 1%-10% with seaweed plants concentration, and the seaweed plants after the salt acid treatment is processed into Powdered, meter by weight proportion, the umber of described hydrochloric acid solution be the seaweed plants umber 5-20 doubly;
B, crust amine is mixed with dilute acid soln, count by weight proportion, crust amine accounts for 0.5-5 part in per 100 parts, remaining is the umber of dilute acid soln, mixes the back and becomes crust amine dilute acid soln, crust amine dilute acid soln is mixed the back pressurization extrude with Powdered seaweed plants in the steps A, count by weight proportion, crust amine dilute acid soln accounts for 95.0-99.5 part in per 100 parts, and remaining is the umber of seaweed plants, and described dilute acid soln is that concentration is the aqueous acetic acid of 0.5%-5%;
C, the thing that makes among the step B is added to after concentration is the 0.5%-10% aqueous slkali, precipitate is constantly arranged;
After D, above-mentioned precipitate finish, wash, oven dry makes the seaweed plants sorbing material that crust amine coats under 50 ℃ of-120 ℃ of conditions again.
Further, the preferred proportion of described marine alga and hydrochloric acid solution is 1: 10.
The preferred proportion of described crust amine and aqueous acetic acid is 3: 97.
Described marine alga and crust amine dilute acetic acid solution best in quality proportioning ratio are 2: 98.
Described seaweed plants is the brown alga plant.
Described sorbing material is made graininess.
Further, described sorbing material is applied in the heavy metal ion-containing waste water.
The biological sorbing material that seaweed plants disclosed by the invention and crust amine are formed combines seaweed plants and the crust amine ability of Adsorption of Heavy Metal Ions separately, with after the waste water that contains heavy metal ion contacts, sodium alginate in the seaweed plants can be by salt-forming reaction in conjunction with heavy metal ion, and crust amine can adsorb heavy metal by chelating, seaweed plants closely is coated in the crust amine cheaply simultaneously, and the granular adsorption material of formation can keep its structural stability in wastewater treatment process.
The biological sorbing material that seaweed plants disclosed by the invention and crust amine are formed has used two kinds of reproducible natural biologic materials.They are nontoxic, pollution-free, and convenient sources is resource with marine organisms all, in China abundant natural source is arranged.Both selectivity are good, to the light metal ion such as the K of a large amount of existence
+, Na
+, Mg
2+Deng not adsorbing or weak absorption, therefore having broad application prospects aspect the processing heavy-metal pollution.
Seaweed plants of the present invention is the brown alga plant, comprises that sea-tangle, bulk kelp etc. contain the brown algae plant of alginic acid.
Algae is a kind of widely distributed in the world plant.About 40,000 kinds of global known algae is widely distributed at occurring in nature, and the overwhelming majority is aquatic or is grown in dark surfaces such as rock, corner, tree bar and soil.Marine alga is the plant that is grown in the seawater, and their output height is collected processing easily, is a kind of abundant renewable resource.The occurring in nature seaweed plant can be divided into several big classes such as green alga, red algae and brown alga, and wherein sea-tangle belongs to the brown algae marine alga.The cell of marine alga has hollow structure, can very fast moisture expantion after meeting water.The cell membrane of marine alga is to be made of the network structure that cellulosic microfibril forms, and includes abundant polysaccharide, as pectin, wood sugar, mannose, alginic acid and lichenic acid, for cell provides protective effect.
Alginic acid is the main component in the brown algae plant, and its content is approximately 20-40%.Form water-fast salt because alginic acid can combine with heavy metal ion, it plays a major role in the process of marine alga Adsorption of Heavy Metal Ions.
The preparation method of the biological sorbing material that seaweed plants disclosed by the invention and crust amine are formed at first carries out preliminary treatment with hydrochloric acid solution to seaweed plants, lose the swelling behavior in water after making the alginic acid that contains in the seaweed plants protonated, then seaweed plants is pulverized, it can be evenly dispersed in the crust amine aqueous solution.The dispersion of Xing Chenging is after splashing into or clamp-on in the aqueous slkali like this, and crust amine is precipitated, and the seaweed plants that is dispersed in the solution is covered by in the crust amine, and the alginic acid in the seaweed plants is converted into water miscible sodium alginate simultaneously.Fig. 1 has shown the structural representation of the biological sorbing material that seaweed plants of the present invention and crust amine are formed.
The biological sorbing material that seaweed plants disclosed by the invention and crust amine are formed is remarkable to the waste water treatment effect that contains heavy metal ion.Crust amine can pass through the chelating Adsorption of Heavy Metal Ions, and the sodium alginate in the seaweed plants can be by forming water-fast salt in conjunction with heavy metal ion, and its adsorbed heavy metal ion can be separated from waste water easily.
Description of drawings
The structural representation of the biological sorbing material that Fig. 1 seaweed plants and crust amine are formed;
Fig. 2 adds behind the natural sea-tangle in the solution copper ion concentration to scheme over time;
Fig. 3 adds behind the sea-tangle of the sea-tangle of salt acid treatment and naoh treatment in the solution copper ion concentration to scheme over time;
Fig. 4 three main laminaria samples are to the adsorbance comparison diagram of copper ion;
Wherein, 1, crust amine; 2, graininess seaweed plants.
The specific embodiment
The invention will be further described below by example.
Embodiment one, and the processing technology of the biological sorbing material of present embodiment brown alga comprises the steps:
A, be 1% hydrochloric acid solution immersion treatment with concentration with the brown alga plant, and the brown alga plant after the salt acid treatment is processed into Powdered, meter by weight proportion, the umber of described hydrochloric acid solution is 5 times of seaweed plants umber;
B, crust amine is mixed with dilute acid soln, count by weight proportion, crust amine accounts for 0.5 part in per 100 parts, remaining is the umber of dilute acid soln, mixes the back and becomes crust amine dilute acid soln, crust amine dilute acid soln is mixed the back pressurization extrude with Powdered seaweed plants in the steps A, count by weight proportion, crust amine dilute acid soln accounts for 99.5 parts in per 100 parts, and remaining is the umber of seaweed plants, and described dilute acid soln is that concentration is 0.5% aqueous acetic acid;
C, the thing that makes among the step B is added to after concentration is 0.5% aqueous slkali, precipitate is constantly arranged;
After D, above-mentioned precipitate finish, wash, oven dry makes the brown alga plant absorptive material that crust amine coats under 50 ℃ of conditions again, further sorbing material is made graininess.
Described sorbing material is applied in the heavy metal ion-containing waste water.
Embodiment two, and the processing technology of present embodiment seaweed bio sorbing material comprises the steps:
A, be 10% hydrochloric acid solution immersion treatment with seaweed plants concentration, and the seaweed plants after the salt acid treatment is processed into Powdered, meter by weight proportion, the umber of described hydrochloric acid solution is 20 times of seaweed plants umber;
B, crust amine is mixed with dilute acid soln, count by weight proportion, crust amine accounts for 5 parts in per 100 parts, remaining is the umber of dilute acid soln, mixes the back and becomes crust amine dilute acid soln, crust amine dilute acid soln is mixed the back pressurization extrude with Powdered seaweed plants in the steps A, count by weight proportion, crust amine dilute acid soln accounts for 95.0 parts in per 100 parts, and remaining is the umber of seaweed plants, and described dilute acid soln is that concentration is 5% aqueous acetic acid;
C, the thing that makes among the step B is added to after concentration is 10% aqueous slkali, precipitate is constantly arranged;
After D, above-mentioned precipitate finish, wash, oven dry makes the seaweed plants sorbing material that crust amine coats under 120 ℃ of conditions again, further sorbing material is made graininess.
Described sorbing material is applied in the heavy metal ion-containing waste water.
Embodiment three, and the processing technology of present embodiment seaweed bio sorbing material comprises the steps:
A, be 5% hydrochloric acid solution immersion treatment, and be processed into the seaweed plants after the salt acid treatment Powdered seaweed plants concentration; Count by weight proportion, the umber of described hydrochloric acid solution is 10 times of seaweed plants umber;
B, crust amine is mixed with dilute acid soln, count by weight proportion, crust amine accounts for 3 parts in per 100 parts, remaining is the umber of dilute acid soln, mixes the back and becomes crust amine dilute acid soln, crust amine dilute acid soln is mixed the back pressurization extrude with Powdered seaweed plants in the steps A, count by weight proportion, crust amine dilute acid soln accounts for 98 parts in per 100 parts, and remaining is the umber of seaweed plants, and described dilute acid soln is that concentration is 2% aqueous acetic acid;
C, the thing that makes among the step B is added to after concentration is 5% aqueous slkali, precipitate is constantly arranged;
After D, above-mentioned precipitate finish, wash, oven dry makes the seaweed plants sorbing material that crust amine coats under 90 ℃ of conditions again, further sorbing material is made graininess.
Described sorbing material is applied in the heavy metal ion-containing waste water.
Test one, the sea-tangle water is fully soaked the impurity and the hydrotrope (natural sea-tangle) that the surface is removed in the back.In order to remove the metal ion that self contains in the sea-tangle, be the sea-tangle after the washing that with the running water cleaning, the sample that obtains like this was the sea-tangle (sea-tangle after the pickling) after the salt acid treatment again after 2.5% aqueous hydrochloric acid solution soaked 24 hours with concentration.The 0.6g dissolution of sodium hydroxide in 100mL water, sea-tangle after the acid treatment of adding 10g salt, fully mix the back oven dry, make the alginic acid in the sea-tangle convert sodium alginate to, the sample that obtains after the drying is the sea-tangle (sea-tangle after the alkalization) of naoh treatment, be cut into the graininess sample that diameter is about 2mm behind three kinds of sample dryings on disintegrating apparatus.
Respectively get above-mentioned three kinds of sample 1g, adding the 1000mL copper ion concentration respectively is 124.0mg.L
-1The aqueous solution, after 0,0.5,1,3,8,24 hour gets 10mL solution respectively to be diluted to 1000mL with the content of copper ion in the Atomic Absorption Spectrometry solution.
Fig. 2 has shown and has added behind the natural sea-tangle in the solution copper ion concentration over time.As can be seen, behind the 30min after adding sea-tangle, the concentration of copper ion is from 124.0mg.L in the solution
-1Quickly fall to 20.1mg.L
-1In whole 24 hour testing time scope, the concentration of copper ion descended rapidly in the incipient stage in the solution, but rose to some extent subsequently, tended to balance at last.
Behind the sea-tangle water absorption and swelling, the water-soluble substances in the sea-tangle oozes out from sea-tangle as low-molecular-weight sodium alginate, polysaccharide etc., enters solution.Solution around the sodium sulphate that copper sulphate and sodium alginate reaction back generate also enters.Sea-tangle some tiny fragments of surface enter solution because the stirring of solution also breaks away from from sea-tangle.After these materials enter solution, stablized the copper ion in the solution, slowed down adsorption rate, made that the concentration of copper ion presents ascendant trend in the solution.After through long contact, the reaction in the whole system reaches balance, and the water-soluble substances that enters in the solution is combining back generation condensation product with copper ion, thereby reduces the concentration of copper ion in the solution.
Fig. 3 has shown behind the sea-tangle of the sea-tangle that adds the salt acid treatment and naoh treatment that copper ion concentration over time in the solution.With after the salt acid treatment, the alginic acid in the sea-tangle is converted into alginic acid from the calcium salt and the sodium salt of alginic acid sea-tangle, and alginic acid is a kind of weak organic acid, with copper sulphate in the solution difficulty react.So the alginic acid after the salt acid treatment is poorer than natural sea-tangle to the absorption property of copper ion.
Behind the naoh treatment sea-tangle, the alginic acid in the sea-tangle is converted into sodium alginate, can high level expansion behind the chance water.This sample is very fast to the absorption of copper ion, and the copper ion concentration in the solution descends rapidly.
Fig. 4 has shown the different adsorption capacity of three main laminaria samples.Sea-tangle after natural sea-tangle, the salt acid treatment and the sea-tangle after the naoh treatment are respectively 59.3,38.6 and 88.0mg.g to the adsorbance of copper ion
-1Rising adsorbing in this presentation of results marine alga is alginic acid, and the marine alga after the alkalization, alginic acid wherein is converted into water miscible sodium alginate, and sodium alginate has improved the ability of sea-tangle absorbing copper ion widely.
The experiment two, pulverize after the sea-tangle drying after the acid treatment, 1.5,3,5,7.5,10g crust amine is dissolved in 300mL respectively and contains in the water of 2 gram glacial acetic acid, add 13.5,12.0,10,7.5 and 5 gram sea-tangles respectively by the prescription in the table 1, mixing the back, to splash into 1000mL concentration by funnel be 1% sodium hydrate aqueous solution, and the crust amine that obtains coats the seaweed plants particle and dries after washing.
Table 1. crust amine coats the preparation condition of seaweed plants
| Sample | Sea-tangle after the salt acid treatment, g | Glacial acetic acid, g | Water | Crust amine, |
| 1 | 13.5 | 2 | 300ml | 1.5 |
| 2 | 12.0 | 2 | 300ml | 3 |
| 3 | 10 | 2 | |
5 |
| 4 | 7.5 | 2 | 300ml | 7.5 |
| 5 | 5 | 2 | |
10 |
Respectively get above-mentioned sample 1g, adding the 1000mL copper ion concentration respectively is 242.4mg.L
-1The aqueous solution, got 10mL solution in 24 hours respectively and be diluted to behind the 1000mL content with copper ion in the Atomic Absorption Spectrometry solution.Table 2 has shown the adsorption capacity of different samples.
The different crust amine of forming of table 2. coat the adsorption capacity of seaweed plants particle to copper ion
| Sample | Copper ion concentration, mg.L -1 | Adsorption capacity, mg. |
| 90% sea-tangle: 10% crust amine | 141.2 | 101.2 |
| 80% sea-tangle: 20% crust amine | 135.5 | 106.9 |
| 66.7% sea-tangle: 33.3% crust amine | 130.5 | 111.9 |
| 50% sea-tangle: 50% crust amine | 100.1 | 142.3 |
| 33.4% sea-tangle: 66.6% crust amine | 97.9 | 144.5 |
Respectively get the above-mentioned sample of 1g again, adding the 1000mL zinc ion concentration respectively is 253.6mg.L
-1The aqueous solution, got 10mL solution in 24 hours respectively and be diluted to behind the 1000mL content with zinc ion in the Atomic Absorption Spectrometry solution.Table 3 has shown the adsorption capacity of different samples.
The different crust amine of forming of table 3. coat the adsorption capacity of seaweed plants particle to zinc ion
| Sample | Zinc ion concentration, mg.L -1 | Adsorption capacity, mg. |
| 90% sea-tangle: 10% crust amine | 170.6 | 83 |
| 80% sea-tangle: 20% crust amine | 163.4 | 90.2 |
| 66.7% sea-tangle: 33.3% crust amine | 102.7 | 150.9 |
| 50% sea-tangle: 50% crust amine | 125.4 | 128.2 |
| 33.4% sea-tangle: 66.6% crust amine | 156.2 | 97.4 |
Respectively get the above-mentioned sample of 1 gram again, adding the 1000mL nickel ion concentration respectively is 336.1mg.L
-1The aqueous solution, got 10mL solution in 24 hours respectively and be diluted to behind the 1000mL content with nickel ion in the Atomic Absorption Spectrometry solution.Table 4 has shown the adsorption capacity of different samples.
The different crust amine of forming of table 4. coat the adsorption capacity of seaweed plants particle to nickel ion
| Sample | Nickel ion concentration, mg.L -1 | Adsorbance, |
| 90% sea-tangle: 10% crust amine | 210.5 | 125.6 |
| 80% sea-tangle: 20% crust amine | 206.7 | 129.4 |
| 66.7% sea-tangle: 33.3% crust amine | 228.3 | 107.8 |
| 50% sea-tangle: 50% crust amine | 191.8 | 144.3 |
| 33.4% sea-tangle: 66.6% crust amine | 195.6 | 140.5 |
Copper, zinc and nickel are several metal ion species commonly used in the electroplating industry.Table 1-4 shows that the sorbing material that sea-tangle and crust amine are processed by above-mentioned all proportions all has good adsorption property, show simultaneously utilize carrier by chemical method with biological sorbing material after preliminary treatment is fixing, sorbing material absorption mechanical strength and chemical stability strengthen, life cycle prolongs, can improve the degree of depth of wastewater treatment and efficient, the loss in the circulation of minimizing absorption-desorption.
The biological sorbing material that the present invention is made up of seaweed plants and crust amine combines seaweed plants and the crust amine ability of Adsorption of Heavy Metal Ions separately, with after the waste water that contains heavy metal ion contacts, sodium alginate in the seaweed plants can be by salt-forming reaction in conjunction with heavy metal ion, and crust amine can adsorb heavy metal by chelating, seaweed plants closely is coated in the crust amine cheaply simultaneously, and the granular adsorption material of formation can keep its structural stability in wastewater treatment process.
Claims (7)
1, the preparation method of the biological sorbing material of a kind of seaweed plants and crust amine composition is characterized in that comprising the steps:
A, be the hydrochloric acid solution immersion treatment of 1%-10% with seaweed plants concentration, and the seaweed plants after the salt acid treatment is processed into Powdered, meter by weight proportion, the umber of described hydrochloric acid solution be the seaweed plants umber 5-20 doubly;
B, crust amine is mixed with dilute acid soln, count by weight proportion, crust amine accounts for 0.5-5 part in per 100 parts, remaining is the umber of dilute acid soln, mixes the back and becomes crust amine dilute acid soln, crust amine dilute acid soln is mixed the back pressurization extrude with Powdered seaweed plants in the steps A, count by weight proportion, crust amine dilute acid soln accounts for 95.0-99.5 part in per 100 parts, and remaining is the umber of seaweed plants, and described dilute acid soln is that concentration is the aqueous acetic acid of 0.5%-5%;
C, the thing that makes among the step B is added to after concentration is the 0.5%-10% aqueous slkali, precipitate is constantly arranged;
After D, above-mentioned precipitate finish, wash, oven dry makes the seaweed plants sorbing material that crust amine coats under 50 ℃ of-120 ℃ of conditions again.
2, the preparation method of the biological sorbing material of seaweed plants according to claim 1 and crust amine composition, it is characterized in that: the preferred proportion of described marine alga and hydrochloric acid solution is 1: 10.
3, the preparation method of the biological sorbing material of seaweed plants according to claim 1 and 2 and crust amine composition, it is characterized in that: the preferred proportion of described crust amine and aqueous acetic acid is 3: 97.
4, the preparation method of the biological sorbing material of seaweed plants according to claim 3 and crust amine composition, it is characterized in that: described marine alga and crust amine dilute acid soln best in quality proportioning ratio are 2: 98.
5, the preparation method of the biological sorbing material of seaweed plants according to claim 1 and crust amine composition, it is characterized in that: described seaweed plants is the brown alga plant.
6, the preparation method of the biological sorbing material of seaweed plants according to claim 1 and crust amine composition, it is characterized in that: described sorbing material is made graininess.
7, the application of the biological sorbing material of forming according to the described seaweed plants of above-mentioned arbitrary claim and crust amine, it is characterized in that: described sorbing material is applied in the heavy metal ion-containing waste water.
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| CN102500334A (en) * | 2011-11-07 | 2012-06-20 | 广东轻工职业技术学院 | Ammonium thiocyanate modified seaweed biotype absorbent and preparation method and application thereof |
| CN104435001A (en) * | 2014-11-22 | 2015-03-25 | 毛华养 | Extraction method for kelp organic iodine |
| CN104591334B (en) * | 2014-12-18 | 2016-06-29 | 天津三生生物科技有限公司 | A kind of method of Porphyridium cruentum extracellular polysaccharide adsorbing metal ions |
| CN110064381A (en) * | 2019-04-30 | 2019-07-30 | 广州大学 | A kind of alginate complex microsphere and its preparation method and application of efficient removal contents of many kinds of heavy metal ion |
| CN112759184B (en) * | 2020-12-17 | 2022-12-20 | 十堰碧蓝环保科技有限公司 | Micro-plastic purification and separation system in hazardous waste liquid |
| CN113331141A (en) * | 2021-06-16 | 2021-09-03 | 临沂大学 | Method for improving tensile mechanical property of silk and silk with high tensile property |
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